Certain beta-ketoethyl pyridinium compounds



United States Patent 3,511,849 CERTAIN BETA-KETOETHY L PYRIDINIUM COMPOUNDS Burton D. Wilson, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Application Aug. 9, 1967, Ser. No. 659,316,

now Patent No. 3,403,039, which is a division of application Ser. No. 378,949, June 29, 1964, now Patent No. 3,345,177, dated Oct. 3, 1967. Divided and this application Jan. 22, 1968, Ser. No. 699,359

Int. Cl. C07d 31/42 U.S. Cl. 260-296 4 Claims ABSTRACT OF THE DISCLOSURE Gelatin coating compositions containing a hardening amount of a beta-ketoethyl onium salt, such as 3,8-decanedione-l, l0-bis(pyridinium perchlorate), 3,8-decanedione- 1,IO-bis(triphenylphosphonium perchlorate) and 3-pentanone-1,5-bis(pyridinium perchlorate), for example. The beta-ketoethyl onium salts are new compounds.

This application is a division of copending US. patent application Ser. No. 659,316, filed Aug. 9, 1967 (now Pat. No. 3,403,039), which in turn is a division of US. patent application Ser. No. 378,949, filed June 29, 1964 (now US. Pat. No. 3,345,177, issued Oct. 3, 1967).

This invention relates to gelatin coating compositions containing beta-ketoethyl onium salts as hardeners therein.

Various compounds have been suggested as hardeners for gelatin but in many cases those hardeners have exhibited undesirable photographic effects or have been prone to wander from the layers in which they are placed. Some compounds considered as hardening agents have been objectionable because of their adverse physiological properties.

One object of my invention is to provide .gelatin compositions containing compounds having a good hardening effect on the gelatin after forming coatings therefrom, particularly in preparing photographic products. Another object of my invention is to provide for the hardening of gelatin with compounds relatively free from undesirable photographic effects. A further object of my invention is to provide gelatin hardeners without undesirable physiological properties. A still further object of my invention is to provide gelatin coating compositions containing therein beta-ketoethyl onium salts as hardeners for the gelatin. Other objects of my invention will appear herein.

I have found that compositions comprising gelatin and a beta-ketoethyl onium salt are useful for obtaining coatings or layers which are resistant to the effects of hot water and to swelling. The compounds which are useful as gelatin hardeners in accordance with my invention are identified by the following formula:

where X is an acid anion such as halide or perchlorate. B+ represents a nitrogen, sulfur or phosphorus onium salt residue, such as ammonium, pyridinium, N-methylpiperidinium, sulfonium or hosphonium. m=0 or 1. A is a divalent linkage selected from the group consisting of (CR per se \and (CR in which at least one CR unit is replaced by a replacement selected from the group consisting of CR=CR, O, S-, arylene and cycloalkylene radicals, R being selected from the group consisting of H and alkyl groups of 1-4 carbon atoms. 7

The onium residue B+ may be one of the following:

(1) Pyridinium, either unsubstituted or containing common substituent groups as for example lower alkyl, hydroxyalkyl, benzyl, or the like.

3,511,849 Patented May 12, 19.70

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(2) Trialkylammonium in which the alkyl groups are selected from those of l to 8 carbon atoms or in which two of the alkyl groups form with the nitrogen a heterocyclic ring such as piperidinium.

(3) Sulfonium in which the alkyl groups are selected from those of 1 to 8 carbon atoms or from a heterocyclic ring with the sulfur, as for example thiophanium.

(4) Phosphonium (R P+), in which the R groups are selected from phenyl or lower alkyl groups of 1 to 8 carbon atoms.

Most of the hardeners in accordance with the invention may be conveniently prepared from the corresponding beta-haloethyl ketones, using as a solvent either acetonitrile or an excess of the sulfide or tertiary base reactant. In some cases it may be more convenient to prepare such compounds by alkylation of a bis-Mannich base, such as the following:

ona)iNomomoo-) cnzonimon The hardeners employed are new, as well as their compositions with gelatin and with gelatin-containing photo graphic emulsions.

These com-pounds have been found to exhibit strong activity as gelatin hardeners with substantial freedom from undesirable photographic effects and toxicity. Ordinarily, the use of these hardeners involves incorporating them in an aqueous solution of gelatin such as a composition to be used in making photographic products or in a gelatinsilver halide photographic emulsion. The hardener is preferably incorporated in a gelatin composition in a proportion of 0.5l0 percent, based on the weight of the gelatin in the composition.

The following examples illustrate my invention.

EXAMPLE 1 3,8-decanedione-l,10-'bis(pyridinium perchlorate) 4.78 grams of 1,10-dichloro-3,S-decanedione, the preparation of which is described in Example 1 of Burness and Wilson, application Ser. No. 379,018, filed June 29, 1964 (now Pat. No. 3,360,372), was dissolved in 25 ml. of dry pyridine and the solution was heated at 50 C. for one day. After cooling, the product was precipitated by diluting the mass with ether. The precipitate which formed was collected and a yield of 76 percent was noted, the product being the chloride salt. As this material was hygroscopic, it was converted to the perchlorate -by a double decomposition reaction with sodium perchlorate. Recrystallization from water gave colorless crystals of 3,8-decanedione-1,10- bis(-pyridinium perchlorate), having a melting point of 157l58 C.

This material was incorporated in a gelatin-silver bromide photographic emulsion in proportions of 1, 3 and 6 percent, based on the gelatin, and the various samples and a sample of the emulsion without hardener were each coated on cellulose acetate film support at a coverage of 432 mg. of silver and 980 mg. of gelatin per square foot. The emulsion layers containing the hardener prepared by this example exhibited greatly reduced swelling'as compared with the emulsion layer without hardener therein. It was also found that the hardener was readily compatible with the photographic characteristics of theemulsion.

EXAMPLE 2 3,8-decanedione-1,lO-bis (triphenylphosphonium perchlorate) chloride; Being hygroscopic, this salt was converted to the perchlorate using sodium perchlorate and was recrystal v 7 EXAMPLE 3 3, l Z-tetradecanedi ne- 1 l4-bis (pyridinium perchlorate) Example .1 was substantially repeated except that 1,14- dichloro-B,12-tetradecanedione was substituted for the 1, 10,-dichloro-3,S-decanedione. The starting material us d here was prepared as described in Example 4 of application Ser. No. 379,018 of Burness and Wilson filed June 29, .1964. The reaction was carried out for three days and a yield of 98 percent of chloride salt was obtained. This salt was then converted to the perchlorate, which was recrystallized from water. This material melted at 135- 138 C. This material was incorporated in samples of gelatin silver halide photographic emulsion in proportions of 1%, 3% and 6% based on the weight of the gelatin, and layers thereof were compared with a layer of the emulsion having no hardener added thereto. It was found that the emulsion was considerably more resistant to swelling by Water when the hardener, in accordance with my invention was incorporated therein in the various proportions.

EXAMPLE 4 3,8-decanedione-l,10-bis(tetramethylenesulfonium perchlorate) A dibromo decanedione was prepared in the same man nor as Example 1 of Burness and Wilson application Ser. No. 379,018 filed June 29, 1964 but using 49 grams of adipylbromide and 98.3 grams of anhydrous aluminum bromide in 300 ml. of dibromomethane. The product obtained was precipitated with ether and crude dibromo decanedione was obtained in 91% yield. The material was recrystallized to obtain a product melting at 75-76 C. The adipyl bromide used had been prepared by heating a mixture of 292 grams of dry adipic acid and 180 grams of phosphorus tribromide in 200 ml. chlorobenzene at 60-75". The followingday, the unreacted adipic acid was filtered off and the oil obtained was concentrated in vacuo and purified by distillation.

. I 6.56 grams of 1,10-dibromo-3,S-decanedione, prepared as described, was dissolved in 25 ml. of thiolane and the solution was allowed to stand at room temperature. After about four hours the mass had become solid and it was thinned with acetonitrile. The product obtained was collected and converted to the perchlorate by a double decomposition reaction. The product thus obtained, 3,8- decanedio'ne 1,10 bis(tetramethylenesulfonium perchlorate) was purified by a recrystallization from water in proportions of 1', 3 and 6%, based on the gelatin and v the varioussamples were coated out onto cellulose acetate film' support as was a sample of the emulsion without hardener. ..It was found that the layers containing the hardener in accordance with the invention were decidedly more resistant to the effects of sw lling by water than was the emulsion layer without hardener.

: .EXAMPLE 5 Silver -halide photographic emulsions in which the solid portion of the vehicle was composed of 25% gelatin and I 7 5%*- ;0f the sodium-salt of ethyl acrylate-acrylic acid copolyrgierjSOgZQ acrylate to acid) were coated on clear cellulose acetate film base at the rate of 750 mg./sq. ft. In two'cases 'no' hardener was used '(controls) and in the other cases the hardeners designated were used in the proportions shown. The swell properties of the coatings are also indicated:

' CONCENTRATION Percent of Percent of Percent swell Hardener gelatin total vehicle in water *Consisted of 25%gelatin, ethyl acrylateaerylic acid (sodium salt) coated at about 750 mg./sq. ft. on a clear cellulose acetate film support.

R200=3pentanone-l,5-bis (pyridinium perchlorate) R20l=2,2'-terephthaloyl bis (ethyl trimethyl ammonium p.t.s.) R, 202=3,8-di0xodecane-l,10bis(pyridiniu m perchlorate) In the formula B+CH CH CO (ACO),,,CH CH B 2X- representative compounds which are useful hardeners in accordance with the invention are as follows:

ium perchlorate).

N, N'-2,2-hexahydroterephthaloyldiethyD- bis (pyrid'miurn perchlorate) The hardeners in accordance with the invention are useful in both gelatin coating compositions containing no mineral additive or pigment and in those containing a mineral material added thereto such as baryta coatings, silver-halide emulsions, and the like. The-gelatin coating compositions in accordance with the invention are particularly valuable in the preparation of photographic products in which gelatin layers are desired, such as for subbing layers, photographic emulsion layers, overcoatings, antistatic backings, antihalation layers, and the like. As photographic products are subjected to aqueous processing baths, it is especially desirable that the gelatin layers exhibit good resistance to the swelling effects of water. The tests on the swellingof gelatin layers are made on samples which havebeen pro-incubated for three days at F. and 50 percent relative humidity. The percent swell is conveniently measured as the percent vertical swell after five minutes in water at 68 F. using as the base value the thickness of the gelatin layer before immersion.

The hardeners of my invention can be used advantageously in gelatin-silver halide photographic emulsions in combination with other emulsion addenda referred to in the prior art or in emulsions which have been chemically sensitized in accordance with prior art procedures.

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations andmodifications'can be 'eifected within the spirit and scope of the invention as described hereinabove, andas definedin the appended claims.

I claim:'

1. A compound having the following formula:

B+CH CH CO (ACO CHgCHgB 2X" wherein B is the pyridinium radical; m is 0 or 1, A is a a divalent linkage selected from the group consisting of (CH CH CH OCH CH, p-phenylene and p-cyclohexylene and X- is a non-metallic acid anion se- 6 lected from the group consisting of perchlorate and References Cited chlmide- UNITED STATES PATENTS 2. A compound in accordance with claim 1 wherein 3,453,281 7/1969 Burness et a1. m 260 293.4

said compound is 3,8-decanedione-1,10-bis(pyridininm perchlorate) 3. A compound in accordance with claim 1 wherein 5 HENRY JILES Prfmary Exantmer said compound is 3,1Z-tetradecanedione-1,14-bis(pyri ROTMAN: Asslstant Examlnel' dinium perchlorate).

4. A compound in accordance with claim 1 wherein said compound is 3-pentanone-1,5-bis(pyridinium per- 10 240 chlorate). 594, 293.4, 294.7 

